CA2254825A1 - Detergent composition - Google Patents

Abstract

Detergent composition comprising peroxygen bleach, a bleach catalyst, a non-AQA surfactant and an alkoxylated quaternary ammonium (AQA) cationic surfactant.

Description

CA 022~482~ 1998-11-17 Wo 97/43391 PCT/US97/08442 DETERGENT COMPOSITION

T~ 71! Field The present invention relates to a detelgenl composition comprising a peroxygen bleach, a metal-cont~ining bleach catalyst a non-AQA surfactant and an alkoxylated quaternary ammonium (AQA) cationic surfactant.

~ound to the Invention The formulation of laundry detergents and other cleaning compositions plesen~ a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates. Thus, laundry detergents, hard surfacecleaners, shampoos and other personal cleansing compositions, hand dishwashing detelgellts and detergent compositions suitable for use in automatic dishwashers all require the proper selection and combination of ingredients in order to functioneffectively. In general, such deLelgel1l compositions will contain one or more types of surf~rt~nl~ which are designed to loosen and remove different types of soils and stains.
While a review of the literature would seem to in-lieate that a wide selection of surfact~nt~ and surfactant combinations are available to the detergent m~nllf~rtllrer, the reality is that many such ingredients are specialty ch.omicals which are not suitable in low unit cost items such as home-use laundry deLtrge~ . The fact remains that most such home-use products such as laundry detergents still mainly comprise one or more of the conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfact~nt.c, presumably due to economic considerations and the need to formulate compositions which function reasonably well with a variety of soils and stains and a variety of fabrics.

The quick and efficient removal of different types of soils and stains such as body soils, ~- greasy/oily soils and certain food stains, can be problematic. Such soils comprise a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts ~ and proteinaceous matter and are thus notoriously difficult to remove. Low levels of hydrophobic soils and residual stains often remain on the surface of the fabric after washing. Successive washing and wearing coupled with limited hydrophobic soil removal in the wash c~mlin~tes in a build up of residual soil and stain which further CA 022~482~ 1998-ll-17 entraps particluate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy appearance which is perceived as unwearable and discarded by the consumer.
The literature suggests that various nitrogen-contAining cationic surfactants would be useful in a variety of cleaning compositions. Such materials, typically in the form of amino-, amido-, or quaternary ammonium or imidazolinium compounds, are often designed for specialty use. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair. Other nitrogen-cont~ining surfactants are used in some laundry detergents to provide a fabric softening and anti-static benefit. For the most part, however, the commercial use of such materials has been limited by thedifficulty encountered in the large scale manufacture of such compounds. An additional limitation has been the potential precipation of anionic active components of the detergent composition occasioned by their ionic interaction with cationic surfactants.
The aforementioned nonionic and anionic surfactants remain the major surfactant components in today's laundry compositions.

It has now been discovered that certain bis-alkoxylated quaternary ammonium (AQA) compounds can be used in various detergent compositions to boost detergency performance on a variety of soil and stain types, particularly the hydrophobic soil types, commonly encountered. Unexpectedly. it has now been discovered that compositions cont~ining AQA surfactants, peroxygen bleach and a metal-con~;lining bleach catalyst deliver superior cleaning and whiteness performance versus products cont:~ining the technologies alone.

The AQA surfactants of the present invention provide substantial benefits to theformulator, over cationic surfactants previously known. For example, the AQA
surfactants used herein provide marked improvement in cleaning of "everyday"
greasy/oily hydrophobic soils regularly encountered. hIoreover, the AQA surfactants are compatible with anionic surfactants cornrnonly used in detergent compositions such as alkyl sulfate and alkyl benzene sulfonate: incompatability with anionic components of the detergent composition has commonlv been the limiting factor in the use of cationic surfactants previously known. Low levels (as low as 3 ppm in the laundering li4uor) of AQA surfactants gives rise to the benefits described herein. AQA surfactants can be formlllated over a broad pH range from 5 to 1'. The AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable. and therefore easy to handle in a CA 022~482~ 1998-ll-17 manufacturing plant. AQA surfactants with degrees of ethoxylation above S are sometimes present in a liquid form and can therefore be provided as 100% neat materials. In addition to their beneficial h~n~lling properties~ the availability of AQA
surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs. The AQA surfactants are also compatible with various perfume ingredients, unlike some cationic surfactants known in the art.

Bleach catalysts (characterized by the presence of at least one transition metal atom) interact with peroxide bleaching species to form very powerful hydrophilic bleaches.
These bleaches deliver strong benefits on colored hydrophilic stains and hydrophilic everyday soils (i.e., socks). Historical use of bleach catalysts was made difficult because of concerns regarding fabric damage. It has now been found that fabric damage caused by using a ~im~nP~n-?se catalyst. known to cause fabric damage, can be much reduced when the detergent composition comprisies an AQA cationic surfactant.
It is proposed that these cationics adsorb onto fabrics, modifing the surface charge of the fabric and potentially ion-pairing with the activated catalyst to minimi7P or prevent fabric damage.

It is believed that the greasy/oily soils are effectively solubilized by an AQA, thereby allowing access of the hydrophilic catalyst bleach to the colour bodies in the soil (e.g.
entrapped pigments) resulting in improved soil decolouration. The ability of thecompositions described herein to clean both hydrophilic and hydophobic soils results in superior cleaning and whiteness maintenance.

Bacl~round Art U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/cationic surfactant mixtures. U.K. 2,040,990, issued 3 Sept.~ 19~0, to A. P. Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry detergents.

Summarv of the Invention The present invention provides a composition comprising or prepared by combinin~ a peroxygen bleach, a metal-cont;lininP bleach catalyst a non-AQA surfactant and an CA 022~482~ 1998-ll-17 effective amount of an alkoxylated quaternary ammonium (AQA) cationic surfactant of the formula:

R~ /ApR
N\ X
R2' R3 wherein R1 is a linear, branched or substituted Cg-Clg alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety, R2 is a C1-C3 alkyl moiety, R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, A is C1-C4 alkoxy and p is an integer in the range of from 2 to 30.

Detailed Description of the Invention Peroxy~en Bleachin~ A~ent The detergent compositions herein comprise a peroxygen bleaching agent. Such bleaching agents are typically present at levels of from 1% to 30%, more typically from 5% to 20~, of the detergent composition, especially for fabric laundering.
Preferred peroxygen bleaches are perhydrate bleaches. The perhydrate bleach is norrnally incorporated in the form of the perhydrate salt, especially the sodium salt, at a level of from 1% to 40% by weight, more pret'erably from 2% to 30% by weight andmost preferably from 5 % to 25 % by weight of the compositions.
Although the perhydrate bleach itself has some bleaching capability, a superior bleach exists in the peracid formed as a product of the reaction between the hydrogen peroxide released by the perhydrate and a bleach activator. Preformed peracids are also envisaged as a preferred peroxygen bleaching species.
Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The preferred perhydrate salts are norrnally the alkali metal salts. The perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however. the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal t'ormula NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.

CA 022~482~ 1998-ll-17 wo 97/43391 PCTIUS97/08442 Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention. Sodium percarbonate is an addition compound having a forrnula corresponding to 2Na~CO3.3H2O2, and is available commerciaUy as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. The percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.
A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799~ granted to Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.
A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers. not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1.250 micrometers.
Another suitable bleaching agent which can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate. the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydo~ec:~n~ioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740.446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,~12.934 Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al. Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.

Mixtures of bleaching agents are also envisaged.

Bleach Catalyst CA 022~482~ 1998-11-17 The detergent compositions described herein comprise as an essential component a bleach catalyst. The catalysts are comrnonly present in extremely low levels in product, preferably from 0.001 % to 5% by weight, more preferably from 0.01 % to 2%, most preferably from 0.05% to 1%. Preferably the bleach catalyst is a metal-cont~ining, more preferably a transition metal-cont~ining bleach catalyst. The preferred transition metal-cont~ining bleach catalysts are m~n~nece or cobalt-cont~inin~ bleach catalysts.

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or alllminl-m cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylene~ min~tetraacetic acid, ethylenP~ min~tetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243.

Preferred types of bleach catalysts include the m~n~n~se-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, MnIII2(u-o)l( OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(C104)2, MnIV4(u-0)6(1,4,7-triazacyclononane)4-(ClO4)2, MnIIIMnIV4(u-o) 1 (u-OAc)2 (1,4,7-trimethyl- 1,4,7-triazacyclononane)2-(ClO4)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat.
4,246,612 and U.S. Pat. 5.227 084. See also U.S. Pat. 5,194.416 which teaches mononuclear m~ng~nPse (IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-triazacyclononane)(OCH3)3 (PF6).

Still another type of bleach catalyst~ as disclosed in U.S. Pat. 5,114,606, is a water-soluble complex of m~ng~nPse (III), and/or (IV) with a ligand which is a non-carboxylatepolyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol. dulsitol, mannitol, xylithol, arabitol. adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.

CA 022~482~ 1998-ll-17 U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of Ihe formula:

R~ -N=C-B-C=N-R4 wherein R1, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N=C-R2 and R3-C=N-R4 form a five or six-membered ring.
Said ring can further be substituted. B is a bridging group selected from O, S. CR5R6.
NR7 and C =O, wherein RS, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe,-bispyridylmPth~ne and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)C12. Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(II) perchlorate, Co(2,2-bispyridylamine)202C104, Bis-(2,2'-bispyridylamine) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) perchlorate, and mixtures thereof.

Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-den~ate ligands, including N4MnIII(u-o)2MnIvN4)+and [Bipy2MnIII(u-0)2MnIVbipy2~-(clo4)3 While the structures of the bleach-catalyzing m~ng~nese complexes of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation. Likewise, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the man~anese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn ligand species which actually exists. it functions in an apparently catalytic manner to provide improved bleachin~ performances on stubborn stains such as tea, ketchup, coffee. wine. juice.

CA 022~482s 1998-ll-17 Other bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, pub]ication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed m~n~ntqse on aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt). U.S. 4,626,373 (m~ng~n~se/ligand catalyst), U.S. 4,119,~57 (ferric complex catalyst), Gerrnan Pat.
specification 2,054.019 (cobalt chelant catalyst) ('an~di:~n 866,191 (transition metal-cont~ining salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations). and U.S. 4,728~455 (m~n~nese gluconate catalysts).

Other preferred examples include cobalt (III) catalysts having the forrnula:

Co[(NH3)nM mB bT tQqPp] Yy wherein cobalt is in the +3 oxidation state; n is an integer from 0 to S (preferably 4 or S;
most preferably S); M' represents a monodentate ligand: m is an integer from 0 to S
(preferably 1 or 2; most preferably 1); B' represents a bidentate ligand; b is an integer from 0 to 2; T' represents a tridentate ligand; t is 0 or l; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is 0 or 1; and n + m + 2b + 3t + 4q + Sp = 6; Y is one or more appropriately selected counteranions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt, preferred Y are selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and combinations thereof; and wherein further at least one of the coordination sites attached to the cobalt is labile under automatic dishwashing use conditions and the rem~ining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the reduction potential for cobalt (II1) to cobalt (II) under alkaline conditions is less than about 0.4 volts (preferably less than about 0.2 volts) versus a norrnal hydrogen electrode.

Preferred coball catalysts of this type have the formula:

[Co(NH3)n(M )m~ Yy CA 022~482~ 1998-ll-17 wherein n is an integer from 3 to 5 (preferably 4 or 5; most preferably 5); M' is a labile coor~in~ting moiety. preferably selected from the group consisting of chlorine, bromine, hydroxide, water, and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2; most preferably 1); m+n = 6; and Y is an appropriately selected counteranion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3; most preferably 2 when Y is a -1 charged anion), to obtain a charge-balanced salt.

The preferred cobalt catalyst of this type useful herein are cobalt pent~min~ chloride saJts having the forrnula [Co(NH3)sCI] Yy, and especially [Co(NH3)sCl]C12.

More preferred are the present invention compositions which utilize cobalt (III) bleach catalysts having the formula:

[Co(NH3)n(M)m(B)b] Ty wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to the cobalt by one sile: m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt by two sites; b is 0 or 1 (preferably 0), and when b=0, then m+n = 6, and when b= 1, then m=0 and n=4: and T is one or more appropriately selected counteranions present in a number y, where y is an integer to obtain a charge-balanced salt (preferably y is 1 to 3; most preferably 2 when T is a -1 char~ed anion); and wherein further said catalyst has a base hydrolysis rate constant of less than 0.23 M-l s-1 (25~C).

Preferred T are selected from the group consisting of chloride~ iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate. carbonate bromide, PF6-, BF4-, B(Ph)4-, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof.
Optionally, T can be protonated if more than one anionic group exists in T, e.g.~ HPo42-, HCO3-, H2PO4-, etc. Further, T may be selected trom the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g.~ linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES). etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).

The M moieties include, but are not limited to~ for example, F-, S04-2~ NCS-, SCN-, S203-2, NH3, PO43~, and carboxylates (which preferably are mono-carboxylates, but more than one carboxylate may be present in the moiety as long as the binding to the cobalt is by only one carboxylate per moiety, in which case the other carboxylate in the M moiety CA 022s482s 1998-ll-17 may be protonated or in its salt form). Optionally. M can be protonated if more than one anionic group exists in M ~e.g., HPo42-, HC03-, H2PO4-. HOC(O)CH2C(O)O-. etc.) Preferred M moieties are substituted and unsubstituted Cl-C30 carboxylic acids having the formulas:

RC(O)O-wherein R is preferably selected from the group consisting of hydrogen and C1-C30 (preferably Cl-C1g) unsubstituted and substituted alkyl, C6-C30 (preferably C6-C1g) unsubstituted and substituted aryl, and C3-C30 (preferably Cs-C1g) unsubstituted and substituted heteroaryl, wherein substituents are selected from the group consisting of -NR'3, -NR'4+, -C(O)OR', -OR', -C(O)NR'2, wherein R' is selected from the group consisting of hydrogen and C1-C6 moieties. Such substituted R therefore include the moieties -(CH2)nOH and -(CH2)nNR'4+, wherein n is an integer from 1 to about 16,preferably from about 2 to about 10, and most preferably from about 2 to about 5.

Most preferred M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 alkyl, and benzyl. Most preferred R is methyl. Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic. naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric. Iinoleic, lactic, malic, and especially acetic acid.

The B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenyl~l~nin~).

Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-MetalComplexes", Adv. Inor~. Bioinor~. Mech., (1983), , pages 1-94. For example, Table 1 at page 17, provides the base hydrolysis rates (designated therein as koH) for cobalt pens~mine catalysts complexed with oxalate (koH= 2.5 x 10-4 M-l s-1 (25~C)), NCS-(koH= 5.0 x 10-4 M~1 s-1 (25~C)), forrnate (koH= 5.8 x 10-4 M-1 s-l (25~C)), andacetate (koH= 9.6 x 10-4 M-1 s-1 (25~C)). The most preferred cobalt catalyst useful herein are cobalt penl l~mine acetate salts having the formula [Co(NH3)sOAc7 Ty~ wherein CA 022~482~ 1998-11-17 OAc represents an acetate moiety, and especially cobalt pent~mine acetate chloride, [Co(NH3)sOAc]Cl2; as well as [Co(NH3)sOAc](OAc)2: ~Co(NH3)sOAcl(PF6)2:
[Co(NH3)sOAc](SO4); [Co(NH3)sOAc](BF4)2; and [Co(NH3)sOAc](NO3)2 (herein "PAC").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article hereinbefore and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 1043-45;
The Synthesis and Characterization of Inorganic Compounds. W.L. Jolly (Prentice-Hall;
1970), pp. 461-3; Inor~. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982); Inor~. Chem., 18. 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistr~, 56, 22-25 (1952); as well as the synthesis examples provided hereinafter.

As a practical matter, and not by way of limitation, the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium. and will preferably provide from about 0.01 ppm to about 25 ppm,more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions herein will comprise from about 0.0005 % to about 0.2%, more preferably from about 0.004~ to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts. by weight of the cleaning compositions.

Alkoxylated Quaterrlary Ammonium (AQA~ Cationic Surfactant The second essential component of the present invention comprises an effective amount of an AQA surfactant of the formula:
R~ / ApR'1 N\ X
R~/ R3 wherein R1 is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety conr~inin~ from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms; R2 and R3 are each independently CA 022~482~ 1998-ll-17 WO 97/43~9t PcT/uss7/08442 alkyl groups cont~ining from 1 to 3 carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X~ is an anion such as chloride, bromide, methylsulfate~ sulfate to provide electrical neutrality: A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and p is an integer from 2 to 30, preferably 2 to 15, more preferably 2 to 8, most preferably 2 to 4.

AQA compounds wherein the hydrocarbyl substituent R1 is Cg-C12 especially Cg-1o,enhance the rate of dissolution of laundry granules, especially under cold waterconditions, as compared with the higher chain length materials. Accordingly, the Cg-C12 AQA surfactants may be preferred by some formulators. The levels of the AQA
surfactants used tO prepare finished laundry detergent compositions can range from 0.1% to 5%, typically from 0.45% to 2.5%, by weight.

The present invention employs an "effective amount" of the AQA surfactants to improve the performance of cleaning compositions which contain other adjunct ingredients. By an "effective amount" of the AQA surfactants and adjunct ingredients herein is meant an amount which is sufflcient to improve, either directionally or significantly at the 90% confidence level, the perforrnance of the cleaning composition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the forrnulator will use sufficient AQA to at least directionally improve cleaning perforrnance against such stains. Likewise, in a composition whose targets include clay soil. the formulator will use sufficient AQA to at least directionally improve cleaning perforrnance against such soil. Importantly, in a fully-formulated laundry detergent the AQA surfactants can be used at levels which provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the data presented hereinafter.

As noted, the AQA surfactants are used herein in detergent compositions in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning perforrnance. In the context of a fabric laundry composition. such "usage levels" can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine.

For exarnple, in a top-loading, vertical axis U.S.-type automatic washing machine using 45 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 minutes and a wash water temperature of 10~C to 50~C, it is preferred to include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of the AQA surfactant in the wash liquor. On the basis of usage rates of from 50 ml to 150 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.1% to 3.2%, preferably 0.3% to 1.5%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 60 g to 95 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt.) of the AQA
surfactant of from 0.2% to 5.0%, preferably from 0.5% to 2.5%. On the basis of usage rates of from 80g to 100g per load for spray-dried granules (i.e., "fluffy";
density below 650 g/l), this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.1 % to 3.5%, preferably from 0.3% to 1.5%.

For example, in a front-loading, horizontal-axis European-type automatic washingm~rlline using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 minutes and a wash water temperature of 30~C to 95~C, it is preferred to include from 13 ppm tO 900 ppm, preferably from 16 ppm tO 390 ppm. of the AQA surfactant in the wash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load. this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.4% to 2.64%. preferably 0.55% to 1.1%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 40 g to 210 g per wash load, for dense ("compact"~
granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.5 % to 3.5 %. preferably from 0.7 % to 1.5 %. On the basis of usage rates of from 140 g to 400 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.13% to 1.8%, preferably from0.18% toO.76%.

For example, in a top-loading, vertical-axis Japanese-type automatic washing machine using 26 to 52 liters of water in the wash bath, a wash cycle of 8 to lS minutes and a - wash water temperature of 5~C to 25~C, it is preferred to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm~ of the AQA surfactant in the wash liquor.
On the basis of usage rates of from 20 ml to 30 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.25 % to 10% .
preferably 1.5% to 2%, for a heavy-duty liquid laundry detergent. On the basis of CA 022~482~ 1998-ll-17 wo 97/43391 pcTluss7lo8442 usage rates of from 18 g to 35 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.25% to 10%, preferably from 0.5~ to 1.0%. On thebasis of usage rates of from 30 g to 40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.25% to 10%, preferably from 0.5% to 1%.

As can be seen from the foregoing, the amount of AQA surfactant used in a machine-wash laundering context can vary, depending on the habits and practices of the user, the type of washing m~rllin~, and the like. In this context, however, one heretoforeunappreciated advantage of the AQA surfactants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains even when used at relatively low levels with respect to the other surfactants (generally anionics or anionic/nonionic mixtures) in the finished compositions. This is to be distinguished from other compositions of the art wherein various cationic surfactants are used with anionic surfactants at or near stoichiometric levels. In general, in the practice of this invention, the weight ratio of AQA:anionic surfactant in laundry compositions is in the range from 1:70 to 1:2. preferably from 1:40 to 1:6, more preferably from 1:30 to 1:6, most preferably from 1: 15 to 1: 8 . In laundry compositions which comprise bothanionic and nonionic surfactants. the weight ratio of AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, preferably 1:50 to 1:8.

Various other cleaning compositions which comprise an anionic surfactant, an optional nonionic surfactant and specialized surfactants such as betaines, sultaines, amine oxides, and the like, can also be formulated using an effective amount of the AQA
surfact~nt~ in the manner of this invention. Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surfacecleaners, shampoos, personal cleansing bars. Iaundry bars, and the like. Since the habits and practices of the users of such compositions show minimal variation, it is satisfactory to include from 0.25% to 5%~ preferably from 0.45% to 2%, by weight, of the AQA surfactants in such compositions. Again, as in the case of the granular and liquid laundry compositions, the weight ratio of the AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionics.
Preferably~ such cleaning compositions comprise AQA/surfactant ratios as noted immediately above for machine-use laundry compositions.

CA 022~482~ 1998-ll-17 1~

In contrast with other cationic surfactants known in the art, the alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed surt'actant systems which are quite low in nonionic surfactants and which contain, for example, alkyl sulfate surfactants. This can be an important consideration for formulators of detergent compositions of the type which are conventionally desi~ned for use in top loading automatic washing machines, especially of the type used in North America as well as under Japanese usage conditions. Typically, such compositions will comprise an anionic surfactant:nonionic surfactant weight ratio in the range from 25:1 to 1:25, preferably 20:1 to 3:1. This can he contrasted with European-type formulas which typically will comprise anionic:nonionic ratios in the range of 10:1 to 1:10, preferably 5:1 to 1:1.

The preferred ethoxylated cationic surfactants herein can be synthesized using a variety of different reaction schemes (wherein "EO" represents -CH2CH2O- units)~ as follows.

R OH ~ C H3NH~ H,/Cat/Heat Rl N~C 3 EXCESS

,CH3 ~ BASF C~t> Rl N--(EO) --H

Rl N--(EO)I1--H + CH3Cl HEAT~ Rl N--(EO)n--H
l H3 cr ,N--(EO)~H + 2 ,C~ H C t C~ , "DIGLYCOLAMINE"

R I B ( H3 \N--(EO ) H I IEA l' ~ 1~ l N ' (E~O )--H

CA 02254825 1998-ll-17 WO 97t43391 PCT/US97/08442 ~N--(EO)H + n~ BASE CAT CH3~

R Br + 3~N--(EO)n+l H HEAT ~ Rl I + (EO)n+l H
CH3 CH3 Br ... ..

CA 022~482~ 1998-ll-17 Cl--CH2CH~--OH + n~ ~ Cl--C~l,CH O[EO]n--H

CHl R--N~CH + Cl--CH2CH2O[EO]n--H ~ R'~'--CH~CH~O[EO]n--H
CH3 Cl An economical reaction scheme is as follows.

CH, Rl OSO3~Na+ + 3'N--CH7CH2-OH HEAT~ Rl N--C'll,CH,-OH + Na~SO~ + H,O

~--N--CH2CH2-OH + n~ HEAT ~ R--l--C}J-C H,O[Eo]n--~l C}l, CH, Rl N--CH,CH2O[EO]n--H + CH3Cl ~ Rl N--C'H?('I l.O[EO]n--H
C~13 c~l Cl For reaction Scheme 5, the following parameters summarize the optional and preferred reaction conditions herein for step 1. Step 1 of the reaclion is preterably conducted in an aqueous medium. Reaction temperatures are typically in the ran_e of 100-230~C.
Reaction pressures are 50-1000 psig. A base, pref'erahly sodium hydroxide, can be used to react with the HSO4- generated during the reaction. In another mode, an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5: preferably from 5:1 to 1:1.1;
more preferably from 2:1 to 1:1. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble. The product of step 1 is then ethoxylated and quaternized using standard reactions, as shown.

The following illustrates the foregoing for the convenience of the f'ormulator, but is not intended to be limiting thereof.

CA 022~482~ l998-ll-l7 WO 97/43391 PCTrUS97/08442 Preparation of N-(2-hvdroxYethyl)-N-methyldodecYlamine - To a glass autoclave liner is added 156.15 g of sodium dodecyl sulfate (0.5415 moles), 81.34 g of 2-(methylamino)ethanol (1.083 moles), 324.5 g of distilled H2O, and 44.3 g of 50 wt. %
sodium hydroxide solution (0.5538 moles NaOH). The glass liner is sealed into 3 L, stainless steel, rocking autoclave, purged twice with 260 psig nitrogen and then heated to 160-180~C under 700-800 psig nitrogen for 3 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 1 L separatory funnel. The mixture is separated into a clear lower layer, turbid middle layer and clear upper layer. The clear upper layer is isolated and placed under full vacuum (<100 mm Hg) at 60-65~C with mixing to remove any residual water. The clear liquid turns cloudy upon removing residual water as additional salts crystallizes out. The liquid is vacuum filtered to remove salts to again obtain a clear, colorless liquid. After a few days at room temperature, additional salts crystallize and settle out. The liquid is vacuum filtered to remove solids and again a clear, colorless liquid is obtained which remains stable. The isolated clear, colorless liquid is the title product by NMR analysis and is >90% by GC analysis with a typical recovery of ~90%. The amine is then ethoxylated in standard fashion. Quaternization with an alkyl halide to form the AQA
surfactants herein is routine.

According to the foregoing, the following are nonlimiting, specific illustrations of AQA
surt'actants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with diff'ering degrees of ethoxylation.
Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", "EO3.5", and the like.

Desi~nation _1 _2 R3 Alkoxylation AQA-2 C1o-C16 CH3 CH3 EO2 CA 022~482~ 1998-ll-17 AQA-S Clo~C18 CH3 CH3 EO5-8 AQA-7 C14-C16 CH3 C3H7 (EO/PrO)4 AQA-8 C12-C14 CH3 CH3 (PrO)3 AQA-10 Cg-Clg CH3 CH3 EO15 AQA-l l Clo C2H5 C2H5 EO3.5 AQA-12 Clo CH3 CH3 EO2.5 AQA-13 Clo CH3 CH3 EO3.5 AQA-14 Clo C4H9 C4H9 EO30 AQA-lS C8C14 CH3 CH3 EO2 AQA-16 Clo CH3 CH3 EO10 AQA-17 C12-C18 C3Hg C3H7 Bu4 AQA-l9 C8 CH3 CH3 iPr3 AQA-21 C12 CH3 CH3 EO3.5 AQA-22 C12 CH3 CH3 EO4.5 CA 022~482~ 1998-ll-17 wo 97/43391 PCT/US97/08442 Highly preferred AQA compound for use herein are of the formula /(CH,CH~0),-5 H
\N \ X~

wherein Rl is Cg-C1g hydrocarbyl and mixtures thereof, especially Cg-C14 alkyl, preferably Cg, Clo and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted. compounds of the foregoing type include those wherein the ethoxy (CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and [CH2CH(CH30~ units (i-Pr) or n-propoxy units (Pr)~ or mixtures of EO and/or Pr and/or i-Pr units.

Non-AOA Detersive Surfactants In addition to the AQA surfactant, the compositions of the present invention preferably further comprise a non-AQA surfactant. Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.

Anionic Surfactant Nonlimiting examples of anionic surfactants useful herein typically at levels from 1% to 55%, by weight. include the conventional C11-Clg alkyl benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random Clo-C20 alkyl sulfates, the C1o-C1g secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3 M+) CH3 and CH3 (CH2)y(CHOS03 M+) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the C1o-C1g sulfated polyglycosides. the Clo-Clg alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), and the Clo-Clg alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The C12-C1g betaines and sulfobetaines ("sultaines"), C1o-C1g amine oxides. can also be included in the overall compositions. C1o-C20 conventional soaps may also be used. If high sudsing is , CA 022s482s 1998-11-17 desired~ the branched-chain C10-cl6 soaps may be used. Other conventional usefulsurfactants are listed in standard texts.

Nonionic Surfactants Nonlimitin~ examples of nonionic surfactants useful herein typically at levels from 1%
to 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C1o-C1g glycerol ethers.

More specifically, the condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary~ and generally contains from 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group con~inin~ from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon atoms, with from 1 tolO moles, preferably 2 to 7, most preferably 2 to 5~ of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include: TergitolTM 15-S-9 (the condensation product of Cl 1-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensationproduct of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-Cls linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-CIs linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the condensation product of C14-Cls linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the condensation product of C13-Cls alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company: and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred range of HLB in these AE
nonionic surfactants is from 8-11 and most preferred t'rom 8-10. Condensates with propylene oxide and butylene oxides may also be used.

Another class of preferred nonionic surfactants for use herein are the polyhydroxy f'atty acid amide surfactants of the formula.

CA 022~482~ l998-ll-l7 R 2 ~ Z .
O R

wherein R1 is H, or C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight C11 15 alkyl or C1s 17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Typical examples include the C12-C1g and C12-C14 N-methylglucamides. See U.S. 5,194,639 and 5.298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.

Also useful as the nonionic surfactant in the present invention are thealkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21,1986, having a hydrophobic group cont~ining from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group cont~ining from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7 saccharide units. Any reducing saccharide cont~inin~ 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-,4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-,4-, and/or 6- positions on the preceding saccharide units.

The preferred alkylpolyglycosides have the formula:

R20(CnH2nO)t(glYC~sYl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from O to lO, preferably O; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these CA 022~482~ 1998-11-17 Wo 97/43391 PCTIUS97/08442 compounds. the alcohol or alkylpolyethoxy alcohol is forrned first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
The additional glycosyl units can then be attached between their 1-position and the prececling glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-posltlon.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols arealso suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide con-len~t~s being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group cont~ining from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tol5 moles, of ethylene oxide per mole of alkyl phenol.
Commercially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are comrnonly referred toas alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base forrned by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 andwill exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Exarnples of compounds of this type include certain of the commercially-available PluronicTM
surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present inventiom are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylen~ mine. The hydrophobic moiety of these products consists of the reaction product of ethylenf~ minto and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. This CA 022~482~ 1998-ll-17 hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of the comrnercially available TetronicTM compounds, marketed by BASF.

Additional Cationic surfactants Suitable cationic surf~rt~ntc are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Other suitable cationic surfact~ntc include the quaternary ammonium surfactants selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl arnmonium surfactants wherein the rem~ining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Optional Detergent ~n~redients The following illustrates various other optional ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof.
Additional Bleach A~ent The detergent compositions herein may comprise an additional bleaching agent. Such ble~ching agents are typically present at levels of from 1 % to 20%, more typically from 3% to ~5%, of the detergent composition, especially for fabric laundering.

Other suitable bleaching agents include chlorine and photoactivated bleaching agents.
Examples of photoactivated bleaching agents include the sulfonated zinc and/or ahlminl-m phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025 % to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
Bleach Activator CA 022~482~ 1998-ll-17 A preferred component of the composition of the present invention is a bleach activator.
Bleach activators are typically present at levels of from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

Peroxygen bleaching agents, the perborates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid or peracid corresponding to the bleach activator.
Various nonlimiting exarnples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene di~min~ (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

In an alternative plefe.,ed aspect a prefor ned peracid is incorporated directly into the composition. Compositions cont~inin~ mixtures of a hydrogen peroxide source and bleach activator in combination with a preformed peracid are also envisaged Highly preferred amido-derived bleach activators are those of the formulae:

R1N(R5)C(o)R2C(o)L or R1C(o)N(R5)R2C(o)L

wherein Rl is an alkyl group cont~ining from 6 to 12 carbon atoms, R2 is an alkylene cont~inin~ from 1 to 6 carbon atoms, R5 is H or alkyl, aryl. or alkaryl cont~inin~ from 1 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above forrnulae include (6-oct~n~mi(lo-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-~iec~n~mido-caproyl)oxyberlzenesulfonate, and mixtures thereof as described in U.S.
Patent 4,634,551, incorporated herein by reference.

CA 022~482~ 1998-11-17 Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference. A highly preferred activator of the benzoxazin-type is:

[~N~C~

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

R6--C--N ,CH2 R6--C--N~

wherein R6 is H or an allyl, aryl, alkoxyaryl, or alkaryl group cont~inin~ from 1 to 12 carbon atoms. Highly ~Ic~lled lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Builders CA 022~482S 1998-11-17 Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of mech~nicm~ including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned. Builder level can vary widely depending upon end use and physical form of the composition.
Built deterge,lL~ typically comprise at least 1% builder. Liquid formulations typically comprise 5% to 50%, more typically 5% to 35% of builder. Granular formulations typically comprise from 10% to 80%, more typically 15% to 50% builder by weight of the detergent composition. Lower or higher levels of builders are not excluded. For example, certain detergent additive or high-surfactant formulations can be unbuilt.

Suitable builders herein can be selectPll from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional-structure as well as amorphous-solid or non-structured-liquid types; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
These may be complemPnted by borates, e.g., for pH-buffering purposes, or by sulfates, especially sodium sulfate and any other fillers or carriers which may be i~l.L)o,lant to the en~in~ering of stable surfactant and/or builder-cont~inin~ de~ gel, composltlons.

Builder mixtures, somPtimPs termed "builder systems" can be used and typically comprise two or more conventional builders. optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing qn~ntities of materials herein. In terms of relative qu~ntitiPs of surfactant and builder in the present detergents, preferred builder systems are typically form~ tPd at a weight ratio of surfactant to builder of from 60:1 to 1:80. Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1Ø

CA 022~482~ 1998-ll-17 P-conr~ining detelgelll builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.

Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6: 1 to 3.2: 1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp.
under the tradename BRITESIL~, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, somPtimpsabbreviated "SKS-6", is a crystalline layered ~ mini~lm-free ~-Na2SiOs morphology silicate marketed by Hoechst and is pref~ ,d especially in granular laundry compositions. See preparative methods in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSixO2x+ 1 yH2o wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein. Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ,B and ~ layer-silicate forms. Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

Also suitable for use herein are synthesized crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2O ySiO2.zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in IJ.S.5,427,711, Sakaguchi et al, June 27, 1995.

Suitable carbonate builders include ~lk~linP earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, andother carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.

CA 022~482~ 1998-11-17 Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [MZ(Alo2)z(sio2)v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amorphous, naturally-occurring or synth~ti~lly derived. An allln inosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976. ~ -ed synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-cal}ed Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula:
Nal2[(AlO2)12(SiO2)12] xH2O wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in ~ m.oter.

Suitable organic detergent builders include polycarboxylate compounds, includingwater-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be form~ ted in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithillm, or alkanolammonium salts are plefe-led. Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Larnberti et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S. 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic coll.pouilds, such as those described in U.S. Patents 3,923,679;
3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylen~ min~ tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and CA 022~482~ 1998-ll-17 biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used for hand-laundering operations, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable anti~c~ling plopelLies.

Certain detersive surf~rt~ntc or their short-chain homologs also have a builder action.
For unambiguous forrnula accounting purposes, when they have surfactant capability, these materials are s~lmmPd up as detersive surfactants. Preferred types for builder functionality are illustrated by: 3,3-dicarboxy4-oxa-1,6-h~x~nP(lio~tes and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof.
Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (prefelled), 2-pentadecenylsuccinate. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Fatty acids, e.g., C12-C1g monocarboxylic acids, can also be incorporated into the compositions as surfactantJbuilder materials alone or in combination with the afo~ ,elllioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S.
4,144,226, C~-tchfi~ld et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.

Other types of inorganic builder materials which can be used have the formula (MX)i Cay (CO3)z wherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the equation ~i = 1 1s(xi multiplied by the valence of Mi) + 2y = 2z is s~ti~fiç~ such that the formula has a neutral or "bal~n~ecl" charge. These builders are referred to herein as "Mineral Builders". Waters of hydration or anions other than carbonate may be added provided that the overall charge is b~l~nrec~ or neutral. The charge or valence effects of such anions should be added to the right side of the above equation.
Preferably, there is present a water-soluble cation selected from the group consisting of CA 022~482~ 1998-ll-17 hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixturesthereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred. Nonlimiting examples of noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chro~.late~ nitrate, borate and mixtures thereof. Preferred builders of this type in their simplest forms are selected from the group consisting of Na2Ca(C03)2, K2Ca(C03)2, Na2Ca2(C03)3, NaKCa(C03)2, NaKCa2(C03)3, K2Ca2(C03)3, and combinations thereof. An especially ~ fe.led material for the builder described herein is Na2Ca(C03)2 in any of its crystalline modifications. Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AshcroftineY, Beyerite, Borc~ile, Burbankite, B~t~chliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Fr~n7init~, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, ~h~nn~shite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite. Prefellcd mineral forms include Nyererite, Fairchildite and Shortite.

Enzymes Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric re~Lo,~lion. Suitable enzymes include proteases, amylases, lipases, cellulases~ peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as p~-activity and/or stability optima, thermostability, and stability to active detergents, builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. P-ef~,red detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but CA 022~482~ 1998-ll-17 WO 97/43391 PCT/US97tO8442 are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases.

Enzymes are norrnally incorporated into deL~lge.ll or detelgelll additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware. In practical terms for current commercial ~ aldlions, typicalamounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5 %, preferably 0.01 %-1 % by weight of a co.~ reial enzyme ~lepaldlion. Protease enzymes are usually present in such cornmercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimi7P the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. Iicheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denmark, hereinafter "Novo". The ple~al~lion of this enzyme and analogous enzymes is described in GB
1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE~
from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.

CA 022~482~ 1998-ll-17 In more detail, an especially pIef~lled protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99, + 101, + 103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Raci//u~ arrryloliquefaciens subtilisin, as described in the patent applications of A. Baeck, et al, entitled "Protease-Cont~ining Cleaning Compositions" having US Serial No. 08/322,676, and C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994.

Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;
~APIDASE~, International Bio-Synthetics, Inc. and TERMAMYL~, Novo.
FUNGAMYL'lC from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6S18-6521. Certain preferred embodiments of thepresent compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially irnproved oxidative stability asmeasured against a rel~re.1ce-point of TERMAMYL(~ in cornmercial use in 1993.
These prefell~d amylases herein share the characteristic of being "stability-enh~nred"
amylases, characterized, at a minimllm, by a measurable irnprovement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenP~ minP inbuffered solution at pH 9-10; thermal stability, e.g., at comrnon wash temperatures such as 60~C; or ~lk~linP stability, e.g., at a p~I from 8 to 11, measured versus the above-identified ler~le"ce-point amylase. Stability can be measured using any of the art-disclosed techni~l tests. See, for example, references disclosed in WO 9402597.
Stability-enh~nced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the comrnonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the ~acilll~ a-amylases, regardless of whether one, two or multiple amylase strains are the immP(li~te precursors. Oxidative stability-enh~nced amylases vs. the above-identified reference amylase are preferred for use, especially in CA 022~482~ l998-ll-l7 bleaching~ more preferably oxygen blearhing, as distinct from chlorine bleaching, d~l~rgent compositions herein. Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the Blicheniformis alpha-amylase, known as TERMAMYL(~, or the homologous position variation of a similar parent amylase, such as B. arrryloliquefaciens, B. subtilis, or B.
stearothe~mophilus; (b) stability-enh~n~ecl amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" plesellled at the 207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in automatic dishwashing det~ge inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B. Iicheniformis NCIB8061. Methionine (Met) was identifiedas the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific m--t~nt~, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE(~ and SUNLIGHT(~; (c) particularly p~erell~ d amylases herein include amylase variants having additional modification in the imm~ te parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL(~;~. Other particularly plefelled oxidative stability enh~n~efl amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enh~nre~
amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme mo~lific~ions are ~ccessihle. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 9S/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the detergent compositions of the present invention include a-amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl(~ at a temperature range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Ph~ oba~(~ a-amylase activity assay. (Such Phadebas(~ a-amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are o~-amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated into laundry detergent compositions at a level from 0.00018% to 0.060% pure enzyme by CA 022~482~ 1998-11-17 weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fungal types, preferably having a pH
optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME(~) and CELLUZYME0 (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for deL.,lgelll usage include those produced by microorg~ni~m~
of the Pseudomonas group, such as Pseudomonas stu~zeri ATCC 19.154, as disclosedin GB 1,372,034. See also lipases in J~pqn~ce Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." Other suitable co~ lcl~;ial lipases inc~ude Amano-CES, lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE~) enzyme derived from Humicola lanuginosa and colllnlelcially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. Seealso WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found widespread application as additive for fabric washing products. It is available from Novo Nordisk under the tradename LipolaseTM, as noted above. In order to optimize the stain removal performance of Lipolase, Novo Nordisk have made a number of variants.
As described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount corresponding to CA 022~482~ 1998-11-17 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions cont~ining the AQA surf~t~ntc in the manner disclosed herein, especially when the D96L is used at levels in the range of 50 LU to 8500 LU per liter of wash solution.

Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g., l..,..;all,onate, perborate, hydrogen peroxide, etc., for "solution ble~lling" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, lignin~ce, and haloperoxidases such as chloro- or bromo-peroxidase.
Peroxidase-cont~ining det.,lgent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation into synthetic deLelge, compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genellcor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful forliquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868. Hora et al, April 14, 1981. Enzymes for use in delelgellls can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP
199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving plol~,ases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Enzyme Stabilizin~ System The enzyme-cont~ining compositions herein may optionally also comprise from 0.001 %
to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a m~n--~rtllrer of detergel,t-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calcium and/or m~gnPsium ions in the fini.ch~-~ compositions which provide such ions to the enzymes.
Calcium ions are generally more effective than m~gn~Sium ions and are pl rc..ed herein if only one type of cation is being used. Typical detergent compositions,especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finichPd del~lgent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, r~lci-~m formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing approach is by use of borate species . See Severson, U . S .4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use. Sl~bstitl~tPd boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.

Stabilizing systems of certain cleaning compositions, for example automatic dishwashing compositions, may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under ~lk~linf conditions. While chlorine levels in water may be small, typically in the range from 0.5 ppm to 1.75 ppm, the available chlorine in the CA 022~482~ 1998-11-17 total volume of water that comes in contact with the enzyme, for example during dish-or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in-use is som~tim~s problematic. Since percarbonate has the ability to react with chlorine bleach the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts cont~ining ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
Antioxidants such as carl~anlat~, ascorbate, etc., organic amines such as ethylenP~ min~ot~tracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Likewise, special enzyme inhibition systems can be incorporated such that different enzymes have maximum compatibility. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium pe.~arlonate, as well as phosphate, con~len.ce~l phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be pe~rolllRd by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-cont~ining embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a ch~mi.ct's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as form~ t~, with other reactive ingredients. In relation to the use of arnmonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage.
Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Ragincki et al.

Polymeric Soil Release A~ent Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to3.0% by weight, of the composition.

CA 022~482~ 1998-11-17 WO 97/43391 rCT/US97/08442 Preferred SRA's typica~ly have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washingand rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to lre~ t with SRA to be more easily cleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S.4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active l)rope.lies. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied d~tc,gel,l or detelge~ll additive products.

~lefelled SRA's include oligomeric terephth~l~te esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a tit~nillm(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.

Suitable SRA's include: a sulfonated product of a subst~nti~lly linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephth~l~te ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephth~l~te polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by tr~n~çstçrification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October CA 022~482~ 1998-ll-17 27, 1987 to Gosselink, for example produced from DMT, Me-capped PEG and EG
and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophth~l~te; and the anionic, especially sulfoaroyl, end-cappedterephth~l~tt- esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further cunlplisillg addedPEG, e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephth~l~te or propylene terephth~l~te with polyethylene oxide or polypropylene oxide terephth~l~tt-, see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Rac~-h-r, July 8, 1975;
cellulosic derivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; and the Cl-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al. Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See Eulopeall Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Culll-~leicially available examples include SOKALAN
SRA's such as SOKALAN HP-22, available from BASF, Gerrnany. Other SRA's are polyesters with repeat units cont~ininE 10-15% by weight of ethylene terephth~l~t~
together with 90-80% by weight of polyoxyethylene terephth~l~te, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula (CAP)2(EG/PG)s(T)s(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably termin~ted with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA
preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene-sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the . . ~ . . , CA 022~482~ l998-ll-l7 synthesis pot, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na- dimethyl 5-sulfoisophth~l~te, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, andcombinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nor~ionic cap~ g units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Pl~f~lled of such esters are those of empirical forrnula:
{(CAP)x(EG/PG)y ' (DEG)y "(PEG)y " ' (T)z(SIP)z' (SEG)q(B)m}

wherein CAP, EGIPG, PEG, T and SIP are as defined hereinabove, (DEG) represents di(oxyethylene)oxy units; (SEG) l~p,esellts units derived from the sulfoethyl ether of glycerin and related moiety units; (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomerbackbone; x is from about 1 to about 12; y' is from about 0.5 to about 25; y" is from O
to about 12; y" ' is from O to about 10; y' +y" +y" ' totals from about 0.5 to about 25;
z is from about 1.5 to about 25; z' is from O to about 12; z + z' totals from about 1.5 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y', y", y"', z, z', q and m r~r~Sel1t the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from about 500 to about 5,000.

Plefelled SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydroxypropoxy)eLllanc~llfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]eth~nP,s~lfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as CA 022~482~ 1998-11-17 Wo 97/43391 PCT/US97/08442 (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O3S[CH2CH2O]3.5)-and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

Additional classes of SRA's include (I) nonionic terephth~l~tec using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4,240,918 ~ se et al; (II) SRA's with carboxylate tel,llinal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of theisolated carboxylic acid of trirnellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (III) anionic tereph~h~l~te-based SRA's of the urethane-linked variety, see U.S.
4,201,824, Violland et al; (IV) poly(vinyl caprolactarn) and related co-polymers with monomers such as vinyl pyrrolidone and/or dirnethylarninoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylicmonomers on to sulfonated polyesters; these SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al, DE
2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

CA 022~482~ 1998-ll-17 Clay Soil Removal/Anti-redeposition A~ents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition prope.~ies. Granular detergent compositions which contain these compounds typically contain from 0.01%
to 10.0% by weight of the water-soluble ethoxylates amines; liquid det~l~el,L
compositions typically contain 0.01 % to S % .

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene-p~ . Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of p.efell~,d clay soil removal-antiredeposition agents are the cationic compounds disclosed in EuropeanPatent Application 111,965, Oh and Gosselink, published June 27,1984. Other claysoil removal/antiredeposition agents which can be used include the ethoxylated an~ine polymers disclosed in European Patent Application 111,984, Gosselink, published lune 27,1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4,1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
See U.S. Patent 4,891,160, VanderMeer, issued January 2,1990 and WO 95/32272, published November 30, 1995. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing A~ents Polymeric di~ ing agents can advantageously be utilized at levels from 0.1 % to 7 %, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

CA 022~482~ 1998-11-17 Wo 97/43391 PCT/USg7/08442 Polymeric polycarboxylate materials can be pr~uared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid forrn.
Unsaturated monomeric acids that can be polymerized to forrn suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segments, cont~ining no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from 2,.000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic/maleic-based copolymers may also be used as a ~efell~d component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of suchcopolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to m~ te segments in such copolymers will generally range from 30: 1 to 1: 1, more preferably from 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/m~ te copolymers of this type are known materials which are described in European Patent Application No. 66915, published December15, 1982, as well as in EP 193,360, published September 3, lg86, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

CA 022~482~ 1998-11-17 Another polymeric material which can be included is polyethylene glycol (PEG). PEG
can exhibit dispersing agent perforrnance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 10,000.

Polyaspartate and polygl~ te dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.

Bri~htener Any optical bri~h~ ers or other bri~htening or whitening agents known in the art can be incorporated at levels typically from 0.01% to 1.2%, by weight, into the detergent compositions herein. Collllllclcial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not nPcess~rily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, m~rhin~cyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M.
Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical bright~n~rs which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988.
These brighteners include the PHORWHITE series of brighteners from Verona. Otherbrigl~ f ~ disclosed in this rere;el.ce include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(ben7imi-1~7Ol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[l,2-d]oxazole; and 2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S.
Patent 3,646,015, issued February 29, 1972 to Hamilton.

Dye Transfer Inhibitin~ A~ents CA 022~482~ 1998-11-17 The compositions of the present invention may also include one or more materialseffective for inhibiting the L,~n~rel of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-viny1imi~l~7ole, ~ g~Pse phthalocyanine, peroxidases, and mixtures thereof.
If used, these agents typically comprise from O.Ol % to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of thepolymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. I'~r~-lcd polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imi-l~701e, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures:

O O
(R~ N--(R2)y; =N--(Rl)x (R3)z wherein Rl, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or conlbil~aLions thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be rhf~-l or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferred pKa < 6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random orblock copolymers where one monomer type is an amine N-oxide and the other monomer CA 022~482~ 1998-ll-17 type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an apl)lopliate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as aclass as "PVPVI") are also preferred for use herein. Preferably the PVPVI has anaverage molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons sl~illed in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions cont~ining PVP can also contain polyethylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1. and more preferably from 3:1 to 10:1.

The detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01% to 1% by weight of such optical brighteners.

CA 022~482~ l998-ll-l7 The hydrophilic optical brighteners useful in the present invention are those having the structural formula:
-Rl R2 N~O~ I ~C=C ~ I ~(~N

R2 SO3M SO3M Rl wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forrning cation such as sodium or potassium.

When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is co~ ,e-cially marketed under the tradename Tinopal-UNPA-GXby Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the dete.ge.lL compositions herein.

When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylaminoand M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is co,-ll.,e.cially marketed under the tradename Tinopal SBM-GX by Ciba-Geigy Corporation.

When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino~2,2'-stilben~ llfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradenarne Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or CA 022~482~ 1998-ll-17 PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighlenels work this way because they have high affinity for fabrics in the wash solution and therefole deposit relatively quick on these fabrics. The extent to which bri~hledeposit on fabrics in the wash solution can be defined by a parameter called the"exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

Of course, it will be apl,leciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightn~ss" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.

Ch~ tin~ A~eents The delelgelll compositions herein may also optionally contain one or more iron and/or m~ng~nlose chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aro-matic chelating agents and mixtures therein, all as hereinafter defined. Withoutintt?n-ling to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and m~n~n~se ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylen~o(li~min~tçtrace-tates, N-hydroxyethylethylen~ nil-P~Iiacetates, nitrilotri~cet~tçs, ethylen~ min~
telrdproprionates, triethylenetetr~minf hexacetates, diethylenetriaminepent~cetates, and ethanoldiglycines, alkali metal, ammonium, and substituted amrnonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are perrnitted in detergent compositions, and include ethylen~ min~tçtrakis (methylenephosphonates) as CA 022~482~ 1998-11-17 DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Polyfunctionally-subsliluted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenPdi~minr disuccinate("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycine di~retic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example,insoluble builders such as zeolites, layered silicates.

If utilized, these chelating agents will generally comprise from 0.1% to 15% by weight of the detergent compositions herein. More preferably, if utilized, the ch~!~ting agents will comprise from 0.1% to 3.0% by weight of such compositions.

CA 022~482~ 1998-11-17 Suds Suppressors Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particularimportance in the so-called "high concentration cleaning process" as described in U.S.
4,489,455 and 4,489,574 and in front-loading European-style washing m~c~linçs.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Ch~mic~l Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds ~uppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and arnrnonium and alkanolammoniumsalts.

The detergent compositions herein may also contain non-surfactant suds ~l,p,essors.
These include, for example: high molecular weight hydrocarbons such as paraffin,fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated arnino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldi~minP chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~ining 1 to 24 carbon atoms, propyleneoxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of 40~C and 50~C, and a minimllm boiling point not less thanl 10~C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100~C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, thus, include aliphatic,alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from CA 022~482~ 1998-11-17 WO 97/43391 pcTrus97lo8442 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons Another preferred category of non-surfactant suds suppressors comprises silicone suds ~u~plessors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds ~u~plessors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No.
89307851.9, published February 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

Mixtures of silicone and sil~n~ted silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, B~gin~ki et al, issued March 24,1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressingamount of a suds controlling agent consisting esse~ti~lly of:
(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiOl/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1;
and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primarysilicone suds suppressor is branched/crosslinked and preferably not linear.

CA 022~482~ 1998-11-17 To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary allLiroan, agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mi~ ., components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room telllpe.d~ c of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431~ Huber et al., issued Pebruary 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of }ess than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room ten-~,.,.dture of more than about 2 weight %, preferably more than about 5 weight ~.

The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. ~ere-l~d is a weight ratio of between about 1:1 and 1: 10, most preferably between 1 :3 and 1 :6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not contain polypropyleneglycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones CA 022~482~ l998-ll-l7 disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a Cl-C16 chain. A ~ r~ d alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds ~uy~ ssors typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry or dishwashing m~c~in.os, suds should not form to the extent that they either overflow the washing m~r~lin~ or negatively affect the washing mechanism of the dishwasher. Suds SUp~lcSSOlS, when ll~ili7~d, are preferably present in a "suds suppressing amount. By "suds sup~lessing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry or dishwashing de~lgell~s for use in automatic laundry or dishwashing m~cilin~os.

The compositions herein will generally comprise from 0% to 10% of suds suppressor.
When utili_ed as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5 %, by weight, of the detergent composition.
Preferably, from 0.5 % to 3 % of fatty monocarboxylate suds suppressor is utilized.
Silicone suds suppressors are typically utilized in amounts up to 2.0 % , by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimi7~d and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01% to 1% of silicone suds suppressor is used, more preferably from 0.25 % to 0.5%. As used herein, these weight percentage values include any silica that may be utili_ed in combination with polyorganosiloxane, as well as any optional materials that may be utili_ed. Monostearyl phosphate suds suppressors are generally utili_ed in amounts ranging from 0.1 % to 2 % , by weight, of the composition. Hydrocarbon suds suppressors are typically utili_ed in amounts ranging from 0.01% to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2 %-3 %
by weight of the fini.ch~d compositions.

Alkoxylated Polycarboxvlates CA 022~482~ 1998-ll-17 Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.
Ch~mic~lly, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of 2000 to 50,000. Suchalkoxylated polycarboxylates can comprise from 0.05% to 10%, by weight, of the compositions herein.

Fabric Softeners Various through-the-wash fabric softeners, especially the impalrahle smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued DecPmber 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5%
to 10% by weight in the present compositions to provide fabric softener benefitsconcurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, Perfumes Perfumes and p.,lru~ y ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic ch~ l ingredients, including, but not limited to, aldehydes, ketones, esters. Also included are various natural extracts and esserl~es which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from 0.01 % to 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from 0.0001 % to 90% of a fini~h~d perfume composition.

Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1,Z,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; ionone methyl; ionone CA 022~482~ 1998-11-17 wo 97/43391 PCT/USg7/08442 gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyc}ododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; l-d~dec~n~l, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, con~lPn.~tion products of phenyl acet~ldehyde and indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cin~ aldehyde;
amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
coumarin; clecai~tone g~mm~; cyclopent~ecannlide; 16-hydroxy-9-hex~decen~ ic acid lactone; 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzo-pyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol, S-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol; caryophyllene alcohol;tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate;
and para-(tert-butyl) cyclohexyl acetate.

Particularly plef~lled perfume materials are those that provide the largest odorimprovements in fini.ch-od product compositions cont~ining cellulases. These perfumes include but are not limited to: hexyl cinn~mic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro4, 6, 6, 7, 8, 8-hexamethy 1-cyclopenta-gamma-2 -benzopyrane; dodecahydro-3a,6,6,9a-tetrarnethylnaphtho[2,1b]furan; anisaldehyde; coumarin; cedrol; vanillin;
cyclopent~decanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.

Other perfume materials include esserti~l oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin. Still other perfume chemicals include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and CA 022~482~ 1998-11-17 wo 97/43391 PCT/US97/08442 eugenol. Carriers such as diethylphth~l~te can be used in the ~mi.~h~d perfume compositions.

Other In~redients A wide variety of other ingredients useful in detelgelll compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C1o-C16alkanol~mi~les can be incoll,o,aled into the compositions, typically at 1%-10% levels.
The Clo-C14 monoethanol and rli~th~nl~l amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing optional surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, water-soluble m~gnPsium and/or calcium salts such as MgC12, MgSO4, CaC12 CaSO4, can be added at levels of, typically, 0.1%-2%, to provide additional suds and toenhance grease removal performance.

Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~ining 3%-5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected"
for use in detergents, including liquid laundry detergent compositions.

, CA 022~482~ 1998-11-17 Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol,propanol, and isoplol,anol are suitable. Monohydric alcohols are plcfelled for solubilizing surfactant, but polyols such as those cont~inin~ from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1 ,2-propanediol) can also be used. The compositions may contain from 5 % to 90%, typically 10% to 50% of such carriers.

The detelgel1t compositions herein will preferably be forTn~ ted such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between 6.8 and 9Ø Laundry products are typically at pH 9-1 l .
Tec~niql~es for controlling pH at leco~ nAe~1 usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Granules M~n--fact -re Adding the bis-alkoxylated cationics of this invention into a cru~cher mix, followed by conventional spray drying, helps remove any residual, potentially malodorous, short-chain amine cont~minqntc. In the event the formulator wishes to plepare an admixable particle cont~ining the alkoxylated cationics for use in, for example, a high density granular d~telge"l, it is preferred that the particle composition not be highly ~lk~lin~.
Processes for p,l ~arh1g high density (above 650 g/l) granules are described in U.S.
Patent 5,366,652. Such particles may be forrn~ ted to have an effective pH in-use of 9, or below, to avoid the odor of impurity amines. This can be achieved by adding a small amount of acidity source such as boric acid, citric acid, or the like, or an applop,iate pH buffer, to the particle. In an alternate mode, the prospective problems associated with amine malodors can be masked by use of perfume ingredients, as disclosed herein.

Examples The following examples are illustrative of the present invention, but are not meant to lirnit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.

CA 022~482~ 1998-ll-17 In the following examples, the abbreviated component identifications have the following me~ning~:
LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-Cls linear alkyl sulfate CxyEzS : Sodium Clx-Cly branched alkyl sulfate con(~n.~e~ with z moles of ethylene oxide C45E7 : A C14 15 predomin~ntly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol con~en~ed with an average of 3 moles of ethylene oxide C25E5 : A C12 15 branched primary alcohol con-i~on.~ed with an average of 5 moles of ethylene oxide CocoEO2 : R1.N+(CH3)(C2H4O~)2 with Rl = C12 ~
cl4 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C16-C1g alkyl N-methyl gluc~mide TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A102SiO2)12. 27H20 having a primary particle size in the range from 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula ~ -Na2si2o5 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 20011m and 900~m Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 400~Lm and 1200~1m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) .

CA 022~482~ 1998-ll-17 WO 97/43391 PCTtUS97/08442 Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425,um and 850 ~m MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tr~de~mP
Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the tradename Lipolase Endolase : Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S
PB4 : Sodium perborate tetrahydrate of nominal formula NaBo2.3H2o.H2o2 PBl : Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03 3H2~2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylen~ min~
NACA-OBS : (6 non~n~mido caproyl) oxybenzene sulphonate DTPMP : Diethylene triamine penta (methylene CA 022~482~ l998-ll-l7 phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Co Catalyst : Pent~min~ acetate cobalt (III) salt Mn Catalyst : MnIV2(m-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2as described in U.S. pat. nos 5 246 621 and 5 244 594 Photoactivated : Sulfonated Zinc Phthalocyanine encapsulated in bleach dextrin soluble polymer Bright~n~r 1 : Disodium4,4'-bis(2-sulphostyryl)biphenyl Brighten~or 2 : Disodium4,4'-bis(4-anilino-6-morpholino-1 . 3 . 5 -triazin-2-yl)amino) stilbene-2: 2 ' -disulfonate.
HEDP : l,1-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrrolidone and vinylimitl~7O1e SRA 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephlhaloyl backbone SRA 2 : Diethoxylated poly (1, 2 propylene terephth~l~te) short block polymer~ilicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to~aid dispersing agent of 10:1 to 100:1.
~n the following Examples all levels are quoted as % by weight of the composition.

CA 022~482~ l998-ll-l7 WO 97/43391 PCT/US97tO8442 EXAMPLE I
The following detergent formulations according to the present invention are prepaled, where A and C are phosphorus-cont~ining detergent compositions and B is a zeolite-cont~inin~ detelge"L composition.
B C
Blown Powder ST PP 24.0 - 24.0 Zeolite A - 24.0 C45AS 8.0 5.0 11.0 MA/AA 2.0 4.0 2.0 L A S 6.0 8.0 11.0 TAS 1.5 CocoMeEO2* 1.5 1.0 2.0 Silicate 7.0 3 0 3 0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C 25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 Perfume 0.3 0 3 0 3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4 0 0 TAED 3.0 3.0 1.0 Mn Catalyst 0.3 0.05 0.4 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0 4 Amylase 0.25 0.30 0.15 Dry mixed sodium sulfate 3.0 3.0 5.0 R~l~nre (Moisture &
Miscellaneous) To:100.0 100.0 100.0 CA 022~482~ 1998-11-17 W O 97/43391 PCTrUS97/08442 Density (g/litre) 630 670 670 *The AQA- 1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants AQA-2 through AQA-22 or other AQA
surfactants herein.

EXAMPLE II
The following detergent formulations, according to the present invention are prepared:
G H
Blown Powder Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 13.0 11.0 21.0 C45AS 8.0 7.0 7.0 CocoMeEO2* 1.0 1.0 1.0 Mn Catalyst 0.9 0.7 O.OS
Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP - 0.4 0.4 Spray On C45E7 1.0 1.0 1.0 Dry additives P V P VI/P V N O O.S 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 PBl 1.0 5.0 6.0 Sodium sulfate - 6.0 R~l~nre (Moisture & Miscellaneous) To: 100 100 100 CA 022~482~ 1998-11-17 Wo 97/43391 PCT/US97/08442 *The AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surf~rt~ntc AQA-2 through AQA-22 or other AQA
surf~ct~nt~ herein.

EXAMPLE III
The following high de,lsity and bleach-con~ining detergent formulations, according to the present invention are prepared:
J K L
Blown Powder Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0 0 LAS 3.0 3.0 3.0 CocoMeEO2* l.0 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates TAS 2.0 2.0 l.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0 3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PBl 13.0 7.0 10.0 Mn Catalyst 0.02 0.4 0. l Polyethylene oxide of MW 5,000,000 - - 0.2 Bentonite clay - - l0.0 Protease l.0 l.0 l.0 CA 02254825 1998-ll-17 WO 97/43391 PCI'/US97/08442 Lipase 0.4 0.4 0 4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 R~l~nre (Moisture &
Mi.cce!l~ntoous) To:100.0 100.0 100.0 Density (g/litre) 850 850 850 *The AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surf~t~ntc AQA-2 through AQA-22 or other AQA
surfactants herein.

EXAMPLE IV

The following high density detergent forrnulations according to the present invention are prepared:
M N
Blown Powder Zeolite A 2.5 2 .5 Sodium sulfate 1.0 1.0 CocoMeEO2* 1.5 1.5 Agglomerate C45AS 11.0 14.0 ZeoliteA 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC ~ S 0 5 DTPMP 0.4 0 4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 0-3 SKS 6 13.0 10.0 CA 022~482~ 1998-11-17 Citrate 3.0 1.0 Percarbonate 15.0 15.0 Mn Catalyst 0.03 1.4 SRA 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightlontor 1 0.2 0.2 Brightener 2 0.2 nre (Moisture &
Miscellaneous) To: 100 100 Density (g/litre) 850 850 *The AQA- 1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surf~ct~nt~ AQA-2 through AQA-22 or other AQA
surfa~ t~ntc herein.

Any of the granular detergent compositions provided herein may be tabletted using known tabletting methods to provide detergent tablets.

Modern automatic dishwashing d~le.ge~ can contain bleaclling agents such as hypochlorite sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures thereof; rinse-aids, especially nonionic surf~t~n~c; builders, including zeolite and phosphate builders; low-sudsing detersive surfactants, especially ethylene oxide/propylene oxide condensates. Such compositions are typically in the form of granules or gels.

The following Examples A and B further illustrate the invention herein with respect to a granular phosphate-cont~ining automatic dishwashing detergent.

EXAMPLE V
% by weight of active material INGREDIENTS A B
STPP (anhydrous)1 31 26 CA 022~482~ 1998-11-17 Sodium Carbonate 22 32 Silicate (% Si~2) Surfactant (nonionic) 3 1.5 NaDCC Bleach2 2 --AQA-l * 0.5 1.0 Sodium Perborate 7.79 5 TAED -- 1.5 Co Catalyst 0.2 0.2 Savinase (Au/g) -- 0.04 Termamyl (Amu/g) 425 Sulfate 2;5 25 Perfume/Minors to 100% to 100%
1Sodium tripolyphosphate 2Sodium dichlorocyanurate *The bis-AQA-1 surfactant can be replaced by bis-AQA-2 through bis-AQA-22.

EXAMPLE VI
The following illustrates mixtures of AQA surfact~ntc which can be substituted for the AQA surf~ct~ntc listed in any of the foregoing Examples. As disclosed hereinabove, such mixtures can be used to provide a spectrum of performance benefits and/or to provide cleaning compositions which are useful over a wide variety of usage conditions. Preferably, the AQA surfact~ntc in such mixtures differ by at least 1.5, preferably 2.5-20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-limiting examples of such mixtures are as follows.

Coll,po~ s Ratio (wt.) AQA-1 + AQA-S 1:1 AQA-1 + AQA-10 1:1 AQA-l + AQA-15 1:2 AQA-1 + AQA-5 + AQA-20 1:1:1 AQA-2 + AQA-5 3:1 AQA-5 + AQA-15 1.5:1 AQA-1 + AQA-20 1:3 CA 022~482~ 1998-11-17 wo 97/433s1 PCT/USg7tO8442 Mixtures of the AQA surfa~t~ntc herein with the corresponding cationic sur&ctants which contain only a single ethoxylated chain can also be used. Thus, for example, mixtures of ethoxylated cationic surfact~ntc of the formula R1N+CH3[EO]x[EO]yX~
and R1N+(CH3)2[EOlzX-, wherein R1 and X are as disclosed above and wherein one of the cationics has (x+y) or z in the range 1-5 preferably 1-2 and the other has (x+y) or z in the range 3-100, ~lcÇ~,ldbly 10-20, most preferably 14-16, can be used herein.
Such compositions advantageously provide improved detergency performance (especially in a fabric laundering context) over a broader range of water hardness than do the cationic surfact~ntc herein used individually. It has now been discovered that shorter EO cationics (e.g., E02) improve the cle~ning performance of anionic surfactants in soft water, whereas higher EO cationics (e.g., E015) act to improve hardness tolerance of anionic surf~t~ntc, thereby improving the cle~ning perfo.l,lance of anionic surf~t~ntc in hard water. Conventional wisdom in the del~lgel1~;y artsuggests that builders can optimize the performance "window" of anionic surfact~ntc.
Until now, however, broadening the window to encompass essentially all conditions of water hardness has been impossible to achieve.

EXAMPLE VII
The following illustMtes mixtures of conventional non-AQA surfactants which can be used in combination with the AQA surfactant~ in any of the foregoing Examples, but is not intended to be limiting thereof. The ratios of non-AQA surfactants in the mixtures are noted in parts by weight of the surfactant mixtures.
Mixtures A-C
In~redients Ratios AS*/LAS 1: 1 AS/LAS 10:1 (pref. 4:1) AS/LAS 1:10 (pref. 1:4) *In the foregoing, the primary, subst~nti~lly linear AS surfactant can be replaced by an equivalent amount of secondary AS or branched-chain AS, oleyl sulfate, and/or mixtures thereof, including mixtures with linear, primary AS as shown above. The"tallow" chain length AS is particularly useful under hot water conditions, up to the boil. "Coconut" AS is preferred for cooler wash temperatures.

The mixtures of alkyl sulfate/anionic surfactants noted above are modified by incorporating a nonionic non-AQA surfactant therein at a weight ratio of anionic (total) to nonionic in the range of 25:1 to 1:5. The nonionic surfactant can comprise any of CA 022~482~ 1998-11-17 the conventional classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid amides (less preferred if LAS is present), or nlh~lules thereof, such as those disclosed hereinabove.

Mixtures D-F
AS*tAES 1: 1 AS/AES 10:1 (pref. 4:1) AS/AES 1:10 (pref. 1:4) *Can be replaced by secondary, branched or oleyl AS as noted above.

The mixtures of AS/AES noted above can be modified by incorporating LAS therein at a weight ratio of AS/AES (total) to LAS in the range from 1:10 to 10:1.

The mixtures of AS/AES or their resulting AS/AES/LAS mi~lules can also be combined with nonionic surf~t~ntc as noted for Mixtures A-C at weight ratios of anionic (total) to nonionic in the range of 25:1 to 1:5.

Any of the foregoing l~ s can be modified by the incorporation therein of an amine oxide surfactant, wherein the amine oxide comprises from 1% to 50% of the total surfactant mixture.

Highly preferred combinations of the foregoing non-AQA surf~ct~n~c will comprise from 3% to 60%, by weight, of the total fini~hPd laundry detergent composition. The finich~
compositions will preferably co~ ise from 0.25% to 3.5%, by weight, of the AQA
surfactant.

EXAMPLE VIII
This Example illustrates perfume formulations (A-C) made in accordance with the invention for incorporation into any of the foregoing Examples of bis-AQA-cont~ining de~elgel1~ compositions. The various ingredients and levels are set forth below.

CA 022=,482=, 1998-ll-17 W O 97t43391 PCT~US97/08442 (% Wei~ht) Perfume In~redient A B C
Hexyl cinn~mic aldehyde 10.0 - 5 .o 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde 5.0 5.0 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1, 1,6,7-tetramethyl naphth~lPnP 5 0 10.0 10.0 Benzyl salicylate 5.0 7-acetyl-1, 1 ,3,4,4,6-hPx~mPthyltetralin 10.0 5.0 10.0 Para-(tert-butyl) cyclohexyl acetate 5.0 5.0 Methyl dihydro jasmonate - 5.0 Beta-napthol methyl ether - 0.5 Methyl beta-naphthyl ketone - 0.5 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde - 2.0 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane - 9.5 Dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2, lb]furan 0.1 ~ni.c~ldehyde ~ ~ 0 5 Coumarin - - 5-0 Cedrol - ~ 0-5 Vanillin - - 5.0 Cyclopent~dec~nQlide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 T ~bd~n~lm resin ~ ~ 2.0 Tricyclodecenyl propionate - - 2.0 Phenyl ethyl alcohol 20.0 10.0 27.9 Terpineol 10.0 5.0 Linalool 10.0 10.0 5.0 Linalyl acetate 5.0 - 5.0 Geraniol 5.0 Nerol - 5.0 2-(1,1-dimethylethyl)-cyclohexanol acetate 5 .0 Orange oil, cold pressed - 5.0 Benzyl acetate 2.0 2.0 Orange t~l ~elles - 10.0 Eugenol - 1.0 , Diethylphth~l~t~ 9 5 Lemon oil, cold pressed - - 10.0 Total 100.0 100.0 100.0 The foregoing perfume compositions are admixed or sprayed-onto (typically at levels up to about 2% by weight of the total detergent composition) any of the AQA surfactant-cont~ining cleaning (in~lu-ling bleaching) compositions disclosed herein. Improved deposition and/or retention of the perfume or individual components thereof on the surface being cle~n~-l (or bleached) is thus secured.

Claims (17)

WHAT IS CLAIMED IS:

1. A detergent composition comprising or prepared by combining a peroxygen bleach, a bleach catalyst, a non-AQA surfactant and an effective amount of an alkoxylated quaternary ammonium (AQA) cationic surfactant of the formula:

wherein R1 is a linear, branched or substituted C8-C18 alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety, R2 is a C1-C3 alkyl moiety, R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, A is C1-C4 alkoxy and p is an integer in the range of from 2 to 30.

2. A composition according to Claim 1 wherein the peroxygen bleach is selected from the group consisting of perborate, percarbonate, perphosphate, persilicate or persulfate salts or a preformed peracid.

3. A composition according to either of Claims 1 or 2 wherein the bleach catalyst is a manganese or a cobalt-containing bleach catalyst.

4. A composition according to any of Claims 1 to 3 which is prepared by mixing the non-AQA surfactant and the AQA surfactant.

5. A composition according to any of Claims 1 to 4 wherein the non-AQA surfactant is an anionic surfactant.

6. A composition according to any of Claims 1 to 5 wherein the ratio of AQA to non-AQA
surfactant is from 1:15 to 1:8.

7. A composition according to any of Claims 1 to 6 wherein, said AQA surfactant has the formula R1 is C8-C18 alkyl, R2 is methyl A is an ethoxy or propoxy groups and p is an integer of from 2 to 8.

8. A composition according to any of Claims 1 to 7 wherein, the AQA surfactant has the formula R1 is C8-C18 alkyl, R2 is methyl A is an ethoxy or propoxy groups and p is an integer of from 2 to 4.

9. A composition according to Claim 1 to 8 comprising two or more AQA surfactants, or a mixture of AQA surfactant and a mono-ethoxylated cationic surfactant.

10. A composition according to Claim 1 to 9 comprising two or more non-AQA
surfactants and a mixture of two or more AQA surfactants.

11. A composition according to any of Claims 1 to 10 in a granular, bar, non-aqueous liquid, or tablet form.

12. A method for removing soils and stains by contacting said soils and stains with a detergent composition, or aqueous medium comprising said detergent composition, according to Claims 1 to 10.

13. A method according to Claim 12 to for removing body soil, bleach sensitive soil or surfactant sensitive soil from fabrics.

14. A method according to either of Claims 12 or 13 which is conducted in an automatic machine.

15. A method according to any of Claims 12 to 14 which is conducted by hand.

16. A method for enhancing the deposition or substantivity of perfumes or perfume ingredients onto fabrics or other surfaces, comprising contacting said surfaces with a perfume or perfume ingredient in the presence of an AQA surfactant.

17. A method according to Claim 18 which is conducted using a perfume or perfumeingredient in combination with a detergent composition comprising a AQA.